Organosilicon compound

ABSTRACT

An organosilicon compound represented by the following general formula (1): 
                 
 
wherein R 1  is a hydrogen atom, a phenyl group or a halogenated phenyl group; R 2  is a hydrogen atom or a methyl group; R 3 &#39;s are each a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms; X is a hydrolyzable group; Z 1  is —R 4 —, —R 4 O— or —R 4 (CH 3 ) 2 SiO—, where R 4  is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms; Z 2  is an oxygen atom or a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms; and m is 0, 1 or 2 and n is 0, 1 or 2. When incorporated in silicone compositions, the organosilicon compound acts as a cross-linking agent having well-balanced photopolymerizability and condensation curability.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a novel compound, and more particularly to anorganosilicon compound having curing mechanisms in two ways in which itcures upon photopolymerization and in which it cures upon absorption ofmoisture in air, and capable of acting as a cross-linking agent whenincorporated in silicone compositions.

2. Description of the Prior Art

A variety of photopolymerizable silicone compounds have already beendeveloped, and these are utilized in ultraviolet radiation-curableadhesives and mold-making agents. Also, adhesives having curingmechanisms in two ways in which they cure by photopolymerization and inwhich they cure upon absorption of moisture in air (curing of acondensation type) are in wide use at present. However, cross-linkingagents used in such compositions having curing mechanisms in two waysmake it difficult to balance photopolymerizability with condensationcurability, resulting in materials ill-balanced toward eithercurability.

SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide anorganosilicon compound which can well balance photopolymerizability withcondensation curability when incorporated in silicone compositions.

As a result of extensive studies made on cross-linking agents, thepresent inventors have discovered that the photopolymerizability andcondensation curability can be made well balanced by incorporating atleast two silicon atoms in one molecule to bond a photopolymerizablegroup and a condensation-curable group individually to different siliconatoms so that these groups can take responsibility of thephotopolymerization and the condensation curing, respectively. Thus,they have accomplished the present invention.

More specifically, the present invention provides an organosiliconcompound represented by the following general formula (1):

wherein R¹ is a hydrogen atom, a phenyl group or a halogenated phenylgroup; R² is a hydrogen atom or a methyl group; R³'s may be the same ordifferent and are each a substituted or unsubstituted monovalenthydrocarbon group having 1 to 10 carbon atoms; X is a hydrolyzablegroup; Z¹ is —R⁴—, —R⁴O— or —R⁴(CH₃)₂SiO—, where R⁴ is a substituted orunsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms,and, when the value of 3−m is plural, R⁴'s may be the same or different;Z² is an oxygen atom or a substituted or unsubstituted divalenthydrocarbon group having 1 to 10 carbon atoms; and m is 0, 1 or 2 and nis 0, 1 or 2.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention is described below in detail. The terminology“(meth)acryloyl” herein means acryloyl, methacryloyl, or a combinationthereof.

The organosilicon compound of the present invention is a compoundrepresented by the following general formula (1):

In the formula, R¹ is a hydrogen atom, a phenyl group or a halogenatedphenyl group. R² is a hydrogen atom or a methyl group. R³'s may be thesame or different and are each a substituted or unsubstituted monovalenthydrocarbon group having 1 to 10 carbon atoms, and preferably 1 to 6carbon atoms. In the group represented by R³, the substituted monovalenthydrocarbon group may include halogen-substituted monovalent hydrocarbongroups as exemplified by halogenated alkyl groups such as a chloromethylgroup, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-dichloropropylgroup, a 3-chloropropyl group and a 3,3,3-trifluoropropyl group. Theunsubstituted monovalent hydrocarbon group may include alkyl groups suchas a methyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, an isobutyl group, a tert-butyl group, a pentyl group, ahexyl group, a cyclohexyl group, an octyl group and a decyl group;alkenyl groups such as a vinyl group and an allyl group; aryl groupssuch as a phenyl group and a tolyl group; and aralkyl groups such as abenzyl group and a phenylethyl group. Alkyl groups and aryl groups arepreferred.

X is a hydrolyzable group, which may include, as preferred groups, loweralkoxyl or lower alkenyloxyl groups having 1 to 6 carbon atoms, andparticularly 1 to 4 carbon atoms, as exemplified by alkoxyl groups suchas a methoxyl group, an ethoxyl group, a propoxyl group, a butoxyl groupand a methoxyethoxyl group, and alkenyloxyl groups such as a vinyloxylgroup, an allyloxyl group, a propenoxyl group, an isopropenoxyl groupand a butenyloxyl group, and may further include acyloxyl groups asexemplified by ketoxime groups such as a dimethylketoxime group and amethylethylketoxime group, or acyloxy groups such as acetoxy groups.

Z¹ is a group represented by —R⁴—, —R⁴O— or —R⁴(CH₃)₂SiO—. R⁴ is asubstituted or unsubstituted divalent hydrocarbon group having 1 to 10carbon atoms, and preferably 1 to 6 carbon atoms. When the value of 3−mis plural, R⁴'s may be the same or different. In R⁴, the substituteddivalent hydrocarbon group may include halogen-substituted alkylenegroups such as a chloromethylene group, a dichloromethylene group and achloroethylene group. The unsubstituted divalent hydrocarbon group mayinclude alkylene groups such as a methylene group, an ethylene group, apropylene group and a tetramethylene group, and arylene groups such as aphenylene group.

Z² is an oxygen atom or a substituted or unsubstituted divalenthydrocarbon group having 1 to 10 carbon atoms, and preferably 1 to 6carbon atoms. In Z², the substituted divalent hydrocarbon group mayinclude the same groups exemplified for R⁴ above, and the unsubstituteddivalent hydrocarbon group may include the same groups exemplified forR⁴ above. Letter symbol m is 0, 1 or 2, and n is 0, 1 or 2.

The organosilicon compound represented by the general formula (1) mayinclude, e.g., organosilicon compounds such as organosilanes,organosilalkylenes, organosilarylenes and organosiloxanes having 2 to 5silicon atoms in one molecule, which have in one molecule i) 1 to 3(meth)acryloyloxyl groups and ii) 1 to 3 silicon-bonded hydrolyzablegroups such as silicon-bonded alkoxyl groups or silicon-bondedalkenyloxyl groups.

Specific structures of the organosilicon compound represented by thegeneral formula (1) are shown below. Examples are by no means limited tothese.

The organosilicon compound represented by the general formula (1) can beproduced, e.g., in the following way.

Firstly, it may be produced by a process represented by the followingreaction schemes:

In the above schemes, —CH₂—CH₂—A— corresponds to —Z²— in the generalformula (1), and A is an alkylene group having 1 to 8 carbon atoms,including, e.g., a methylene group, an ethylene group and a propylenegroup.

Alternatively, it may be produced by a process represented by thefollowing reaction schemes:

Method of use and purposes:

The organosilicon compound of the present invention has the twoproperties of photopolymerizability and condensation curability incombination. Hence, it is useful as a cross-linking agent for siliconecompositions, and is used in, e.g., adhesives, coating materials andpotting materials.

EXAMPLES

The present invention is described below in greater detail by givingExamples. The present invention is by no means limited to theseExamples.

Example 1

In a 1-liter four-necked flask having a coiled condenser and athermometer, 135.6 g (0.6 mole) of vinyltriisopropenoxysilane and 200 gof toluene were added, and then heated to 40° C. After the heating, 0.1g of a 2% chloroplatinic acid solution in 2-ethylhexanol was addeddropwise, and 75.9 g (0.66 mole) of dichloromethylsilane was added.After the addition was completed, the reaction was carried out at 60 to70° C. for 1 hour while unreacted dichloromethylsilane was refluxed, andfurther at 80 to 90° C. for 2 hours. After the reaction was completed,using gas chromatography, it was confirmed that thevinyltriisopropenoxysilane reacted completely with thedichloromethylsilane. Its temperature was dropped to about 30° C., andthereafter 133.6 g (1.32 moles) of triethylamine and 0.1 g ofbutylhydroxytoluene were added to the reaction mixture. Next, 171 g(1.32 moles) of hydroxyethyl methacrylate was dropwise added. After theaddition was completed, the resultant mixture was aged at 60° C. for 3hours, and the triethylamine hydrochloride precipitated was filteredoff. After the filtration, the unreacted components were removed byconcentration at 60 to 70° C./665 Pa (5 mmHg) for 2 hours to obtain238.1 g of 1-methylbis(2-methacryloxyethoxy)silyl-2-triisopropenoxysilylethane [the compound of formula (b); yield: 80%).

The above compound was identified by NMR and IR.

NMR: (0.105 ppm, S, 3H, Si—CH₃) (0.65˜0.79 ppm, broad, 4H, —CH₂—CH₂—)(1.79 ppm, S, 9H, O—C—CH₃) (1.90 ppm, S, 6H, ═C—CH₃) (3.86˜4.10 ppm,broad, 8H, —O—CH₂—CH₂—O—) (4.10, 4.26 ppm, d, 6H, O—C═CH₂) (5.52, 6.08ppm, d, 4H, CH₂═C) IR: (2,800˜3,000 cm⁻¹, ^(ν)CH) (1,650 cm⁻¹, ^(ν)C═C)(1,700 cm⁻¹, ^(ν)C═O) (1,150 cm⁻¹, ^(ν)Si—OC)

Example 2

In a 1-liter four-necked flask having a coiled condenser and athermometer, 88.8 g (0.6 mole) of vinyltrimethoxysilane and 200 g oftoluene were added, and then heated to 40° C. After the heating, 0.1 gof a 2% chloroplatinic acid solution in 2-ethylhexanol was added, and75.9 g (0.66 mole) of dichloromethylsilane was added. After the additionwas completed, the reaction was carried out at 60 to 70° C. for 1 hourwhile unreacted dichloromethylsilane was refluxed, and further at 80 to90° C. for 2 hours. After the reaction was completed, using gaschromatography, it was confirmed that the vinyltrimethoxysilane reactedcompletely with the dichloromethylsilane. Its temperature was dropped toabout 30° C., and thereafter 133.6 g (1.32 moles) of triethylamine and0.1 g of butylhydroxytoluene were added to the reaction mixture. Next,171 g (1.32 moles) of hydroxyethyl methacrylate was dropwise added.After the addition was completed, the resultant mixture was aged at 60°C. for 3 hours, and the triethylamine hydrochloride precipitated wasfiltered off. After the filtration, the unreacted components wereremoved by concentration at 60 to 70° C./665 Pa (5 mmHg) for 2 hours toobtain 221 g of 1-methylbis(2-methacryloxyethoxy)silyl-2-trimethoxysilylethane [the compound offormula (h); yield: 84%).

The above compound was identified by NMR and IR.

NMR: (0.105 ppm, S, 3H, Si—CH₃) (0.65˜0.79 ppm, broad, 4H, —CH₂—CH₂—)(1.90 ppm, S, 6H, ═C—CH₃) (3.86˜4.10 ppm, broad, 8H, —O—CH₂—CH₂—O—) (3.3ppm, S, 9H, O—CH₃) (5.52, 6.08 ppm, d, 4H, CH₂═C) IR: (2,800˜3,000 cm⁻¹,^(ν)CH) (1,650 cm⁻¹, ^(ν)C═C) (1,700 cm⁻¹, ^(ν)C═O) (1,150 cm⁻¹,^(ν)Si—OC)

Example 3

In a 1-liter four-necked flask having a coiled condenser and athermometer, 88.8 g (0.6 mole) of vinyltrimethoxysilane and 200 g oftoluene were added, and then heated to 40° C. After the heating, 0.1 gof a 2% chloroplatinic acid solution in 2-ethylhexanol was added, and75.9 g (0.66 mole) of dichloromethylsilane was added. After the additionwas completed, the reaction was carried out at 60 to 70° C. for 1 hourwhile unreacted dichloromethylsilane was refluxed, and further at 80 to90° C. for 2 hours. After the reaction was completed, using gaschromatography, it was confirmed that the vinyltrimethoxysilane reactedcompletely with the dichloromethylsilane. Its temperature was dropped toabout 30° C., and thereafter 133.6 g (1.32 moles) of triethylamine and0.1 g of butylhydroxytoluene were added to the reaction mixture. Next,153 g (1.32 moles) of hydroxyethyl acrylate was dropwise added. Afterthe addition was completed, the resultant mixture was aged at 60° C. for3 hours, and the triethylamine hydrochloride precipitated was filteredoff. After the filtration, the unreacted components were removed byconcentration at 60 to 70° C./665 Pa (5 mmHg) for 2 hours to obtain 209g of 1-methylbis(2-acryloxyethoxy)silyl-2-trimethoxysilylethane [thecompound of formula (g); yield: 84%).

The above compound was identified by NMR and IR.

NMR: (0.105 ppm, S, 3H, Si—CH₃) (0.65˜0.79 ppm, broad, 4H, —CH₂—CH₂—)(1.90 ppm, t, 2H, C═CH) (3.86˜4.10 ppm, broad, 8H, —O—CH₂—CH₂—O—) (3.3ppm, S, 9H, O—CH₃) (5.52, 6.08 ppm, d, 4H, CH₂═C) IR: (2,800˜3,000 cm⁻¹,^(ν)CH) (1,650 cm⁻¹, ^(ν)C═C) (1,700 cm⁻¹, ^(ν)C═O) (1,150 cm⁻¹,^(ν)Si—OC)

Example 4

In a 1-liter four-necked flask having a coiled condenser and athermometer, 135.6 g (0.6 mole) of vinyltriisopropenoxysilane and 200 gof toluene were added, and then heated to 40° C. After the heating, 0.1g of a 2% chloroplatinic acid solution in 2-ethylhexanol was added, and61.7 g (0.66 mole) of dimethylchlorolsilane was added. After theaddition was completed, the reaction was carried out at 60 to 70° C. for1 hour while unreacted dimethylchlorolsilane was refluxed, and furtherat 80 to 90° C. for 2 hours. After the reaction was completed, using gaschromatography, it was confirmed that the vinyltriisopropenoxysilanereacted completely with the dimethylchlorolsilane. Its temperature wasdropped to about 30° C., and thereafter 133.6 g (1.32 moles) oftriethylamine and 0.1 g of butylhydroxytoluene were added to thereaction mixture. Next, 85.4 g (0.66 mole) of hydroxyethyl methacrylatewas dropwise added. After the addition was completed, the resultantmixture was aged at 60° C. for 3 hours, and the triethylaminehydrochloride precipitated was filtered off. After the filtration, theunreacted components were removed by concentration at 60 to 70° C./665Pa (5 mmHg) for 2 hours to obtain 206 g of1-dimethyl(2-methacryloxyethoxy)silyl-2-triisopropenoxysilyl ethane [thecompound of formula (d); yield: 80%).

The above compound was identified by NMR and IR.

NMR: (0.105 ppm, S, 6H, Si—CH₃) (0.65˜0.79 ppm, broad, 4H, —CH₂—CH₂—)(1.80 ppm, S, 3H, C—CH₃) (1.90 ppm, S, 9H, ═C—CH₃) (3.86˜4.10 ppm,broad, 4H, —O—CH₂—CH₂—O—) (4.0, 4.25 ppm, d, 6H, O—C═CH₂) (5.45, 6.1ppm, d, 2H,CH₂═C) IR: (2,800˜3,000 cm⁻¹, ^(ν)CH) (1,650 cm⁻¹, ^(ν)C═C)(1,700 cm⁻¹, ^(ν)C═O) (1,150 cm⁻¹, ^(ν)Si—OC)

Example 5

In a 1-liter four-necked flask having a coiled condenser and athermometer, 152 g (1.0 mole) of tetramethoxysilane and 1 g of tindioctate were added, and then heated to 80° C. Thereafter, 160 g (1.0mole) of acryloxymethyldimethylsilanol was dropwise added. After theaddition was completed, the resultant mixture was aged at 80° C. for 2hours. After the aging, the mixture was distilled under reduced pressureat 92° C./399 Pa (3 mmHg) to obtain 182 g ofacryloxymethyldimethylsiloxytrimethoxysilane [the compound of formula(e); yield: 65%).

The above compound was identified by NMR and IR.

NMR: (0.105 ppm, S, 6H, Si—CH₃) (3.3 ppm, S, 9H, O—CH₃) (3.63 ppm, S,2H, Si—CH₂—) (5.58˜6.35 ppm, broad, 3H, CH₂═CH—) IR: (2,800˜3,000 cm⁻¹,^(ν)CH) (1,650 cm⁻¹, ^(ν)C═C) (1,700 cm⁻¹, ^(ν)C═O) (1,150 cm⁻¹,^(ν)Si—OC)

Example 6

In a 1-liter four-necked flask having a coiled condenser and athermometer, 135.6 g (0.6 mole) of vinyltriisopropenoxysilane and 200 gof toluene were added, and then heated to 40° C. After the heating, 0.1g of a 2% chloroplatinic acid solution in 2-ethylhexanol was added, and75.9 g (0.66 mole) of dichloromethylsilane was added. After the additionwas completed, the reaction was carried out at 60 to 70° C. for 1 hourwhile unreacted dichloromethylsilane was refluxed, and further at 80 to90° C. for 2 hours. After the reaction was completed, using gaschromatography, it was confirmed that the vinyltriisopropenoxysilanereacted completely with the dichloromethylsilane. Its temperature wasdropped to about 30° C., and thereafter 133.6 g (1.32 moles) oftriethylamine and 0.1 g of butylhydroxytoluene were added to thereaction mixture. Next, 211 g (1.32 moles) ofacryloxymethyldimethylsialnol was dropwise added. After the addition wascompleted, the resultant mixture was aged at 60° C. for 3 hours, and thetriethylamine hydrochloride precipitated was filtered off. After thefiltration, the unreacted components were removed by concentration at 60to 70° C./665 Pa (5 mmHg) for 2 hours to obtain 225 g of1-methylbis(acryloxymethyldimethylsiloxy)silyl-2-triisopropenoxysilylethane [the compound of formula (m); yield: 80%).

The above compound was identified by NMR and IR.

NMR: (0.105 ppm, S, 15H, Si—CH₃) (0.65˜0.79 ppm, broad, 4H, —CH₂—CH₂—)(1.90 ppm, S, 9H, ═C—CH₃) (3.63 ppm, S, 2H, Si—CH₂—) (4.10, 4.26 ppm, d,6H, O—C═CH₂) (5.58˜6.35 ppm, broad, 3H, CH₂═CH—) IR: (2,800˜3,000 cm⁻¹,^(ν)CH) (1,650 cm⁻¹, ^(ν)C═C) (1,700 cm⁻¹, ^(ν)C═O) (1,150 cm⁻¹,^(ν)Si—OC)

Example 7

In a 1-liter four-necked flask having a coiled condenser and athermometer, 135.6 g (0.6 mole) of vinyltriisopropenoxysilane and 200 gof toluene were added, and then heated to 40° C. After the heating, 0.1g of a 2% chloroplatinic acid solution in 2-ethylhexanol was added, and61.7 g (0.66 mole) of dichloromethylsilane was added. After the additionwas completed, the reaction was carried out at 60 to 70° C. for 1 hourwhile unreacted dichloromethylsilane was refluxed, and further at 80 to90° C. for 2 hours. After the reaction was completed, using gaschromatography, it was confirmed that the vinyltriisopropenoxysilanereacted completely with the dichloromethylsilane. Its temperature wasdropped to about 30° C., and thereafter 66.8 g (0.66 mole) oftriethylamine and 0.1 g of butylhydroxytoluene were added to thereaction mixture. Next, 105.5 g (0.66 mole) ofacryloxymethyldimethylsialnol was dropwise added. After the addition wascompleted, the resultant mixture was aged at 60° C. for 3 hours, and thetriethylamine hydrochloride precipitated was filtered off. After thefiltration, the unreacted components were removed by concentration at 60to 70° C./665 Pa (5 mmHg) for 2 hours to obtain 213 g of1-dimethyl(acryloxymethyldimethylsiloxy)silyl-2-triisopropenoxysilylethane [the compound of formula (n); yield: 80%).

The above compound was identified by NMR and IR.

NMR: (0.105 ppm, S, 12H, Si—CH₃) (0.65˜0.79 ppm, broad, 4H, —CH₂—CH₂—)(1.90 ppm, S, 9H, ═C—CH₃) (3.63 ppm, S, 2H, Si—CH₂—) (4.10, 4.26 ppm, d,6H, O—C═CH₂) (5.58˜6.35 ppm, broad, 3H, CH₂═CH—) IR: (2,800˜3,000 cm⁻¹,^(ν)CH) (1,650 cm⁻¹, ^(ν)C═C) (1,700 cm¹, ^(ν)C═O) (1,150 cm⁻¹,^(ν)Si—OC)

Example 8

In a 1-liter four-necked flask having a coiled condenser and athermometer, 135.6 g (0.6 mole) of vinyltriisopropenoxysilane and 200 gof toluene were added, and then heated to 40° C. After the heating, 0.1g of a 2% chloroplatinic acid solution in 2-ethylhexanol was added, and75.9 g (0.66 mole) of dichloromethylsilane was added. After the additionwas completed, the reaction was carried out at 60 to 70° C. for 1 hourwhile unreacted dichloromethylsilane was refluxed, and further at 80 to90° C. for 2 hours. After the reaction was completed, using gaschromatography, it was confirmed that the vinyltriisopropenoxysilanereacted completely with the dichloromethylsilane. Its temperature wasdropped to about 30° C., and thereafter 133.6 g (1.32 moles) oftriethylamine and 0.1 g of butylhydroxytoluene were added to thereaction mixture. Next, 153 g (1.32 moles) of hydroxyethyl acrylate wasdropwise added. After the addition was completed, the resultant mixturewas aged at 60° C. for 3 hours, and the triethylamine hydrochlorideprecipitated was filtered off. After the filtration, the unreactedcomponents were removed by concentration at 60 to 70° C./665 Pa (5 mmHg)for 2 hours to obtain 227 g of1-methylbis(2-acryloxyethoxy)silyl-2-triisopropenoxysilylethane [thecompound of formula (a); yield: 80%).

The above compound was identified by NMR and IR.

NMR: (0.105 ppm, S, 3H, Si—CH₃) (0.65˜0.79 ppm, broad, 4H, —CH₂═CH₂—)(1.90 ppm, S, 9H, ═C—CH₃) (3.86˜4.10 ppm, broad, 8H, —O—CH₂—CH₂—O—)(4.10, 4.26 ppm, d, 6H, O—C═CH₂) (5.58˜6.35 ppm, broad, 6H, CH₂═CH—) IR:(2,800˜3,000 cm⁻¹, ^(ν)CH) (1,650 cm⁻¹, ^(ν)C═C) (1,700 cm¹, ^(ν)C═O)(1,150 cm⁻¹, ^(ν)Si—OC)

Example 9

In a 1-liter four-necked flask having a coiled condenser and athermometer, 135.6 g (0.6 mole) of vinyltriisopropenoxysilane and 200 gof toluene were added, and then heated to 40° C. After the heating, 0.1g of a 2% chloroplatinic acid solution in 2-ethylhexanol was added, and61.7 g (0.66 mole) of dimethylchlorolsilane was added. After theaddition was completed, the reaction was carried out at 60 to 70° C. for1 hour while unreacted dimethylchlorolsilane was refluxed, and furtherat 80 to 90° C. for 2 hours. After the reaction was completed, using gaschromatography, it was confirmed that the vinyltriisopropenoxysilanereacted completely with the dimethylchlorolsilane. Its temperature wasdropped to about 30° C., and thereafter 66.8 g (0.66 mole) oftriethylamine and 0.1 g of butylhydroxytoluene were added to thereaction mixture. Next, 76.5 g (0.66 mole) of hydroxyethyl acrylate wasdropwise added. After the addition was completed, the resultant mixturewas aged at 60° C. for 3 hours, and the triethylamine hydrochlorideprecipitated was filtered off. After the filtration, the unreactedcomponents were removed by concentration at 60 to 70° C./665 Pa (5 mmHg)for 2 hours to obtain 206 g of1-dimethyl(2-acryloxyethoxy)silyl-2-triisopropenoxysilylethane [thecompound of formula (c); yield: 80%).

The above compound was identified by NMR and IR.

NMR: (0.105 ppm, S, 6H, Si—CH₃) (0.65˜0.79 ppm, broad, 4H, —CH₂—CH₂—)(1.90 ppm, S, 9H, ═C—CH₃) (3.86˜4.10 ppm, broad, 4H, —O—CH₂—CH₂—O—)(4.10, 4.26 ppm, d, 6H, O—C═CH₂) (5.58˜6.35 ppm, broad, 3H, CH₂═CH—) IR:(2,800˜3,000 cm⁻¹, ^(ν)CH) (1,650 cm⁻¹, ^(ν)C═C) (1,700 cm⁻¹, ^(ν)C═O)(1,150 cm⁻¹, ^(ν)Si—OC)

Application Example

An application example is given below in which the organosiliconcompound of the present invention is used as a cross-linking agent of asilicone composition.

Into a 3-liter Shinagawa mixing stirrer, 1,000 g ofα,ω-hydroxypolydimethylsiloxane having a molecular weight of 20,000, 100g of 1-methylbis(2-methacryloxyethoxy)silyl-2-triisopropenoxysilylethane as a cross-linking agent, 5 g oftetramethylguanidylpropyltrimethoxysilane as a condensation catalyst and20 g of diethoxyacetophenone as a UV-curing catalyst were charged, andwere deaerated and mixed for 20 minutes. After the deaeration, aUV/condensation double-curing composition was obtained. In thefollowing, general properties of cured products obtained in a case inwhich the composition was cured by condensation, a case in which it wascured by UV radiation, and a case in which it was cured by thecombination of UV radiation+condensation.

Measurement of Physical Properties:

-   -   Viscosity:

Measured in accordance with JIS K 6249.

-   -   Tack-free time:

A composition is exposed to an atomosphere in the conditions of 23° C.and 55% RH. The time taken until the surface of the composition get dryto the touch, is measured.

-   -   Mechanical properties of cured products:

Measured in accordance with JIS K 6301.

-   -   Electric properties of cured products:

Measured in accordance with JIS K 6249.

(1) Physical properties of the composition before curing:

TABLE 1 External appearance Pale-yellow and semitransparent Viscosity(25° C.) 2Pa · s Tack-free time (minute) 8

(2) Physical properties after curing:

TABLE 2 Condensation Curing¹⁾ External appearance after curingPale-yellow and semitransparent Hardness (durometer, type A) 27Elongation 60 (%) Tensile strength 0.4 (MPa) Tensile-shear bond strength(glass) 0.1 (MPa) Specific gravity after curing 1.01 Volume resistivity21 (TΩ · m) Dielectric constant (50 Hz) 2.2 Dielectric dissipationfactor (50 Hz) 0.0022 ¹⁾Remarks: Curing conditions: The composition wasleft at 23° C./55% RH for 7 days.

TABLE 3 UV-radiation Curing²⁾ External appearance after curingPale-yellow and semitransparent Hardness (durometer, type A) 24Elongation 20 (%) Tensile strength 0.1 (MPa) Tensile-shear bond strength(glass) 0.1 (MPa) Specific gravity after curing 1.01 Cure depth 3.8 (mm)Volume resistivity 0.8 (TΩ · m) Dielectric constant (50 Hz) 2.55Dielectric dissipation factor (50 Hz) 0.0057 ²⁾Remarks: Curingconditions: The composition was exposed for 5 seconds to a light from ahigh-pressure mercury lamp (80 W/cm) 10 cm distant from the composition.This irradiation was carried out three times.

TABLE 4 Curing by UV Radiation³⁾ + Condensation External appearanceafter curing Pale-yellow and semitransparent Hardness (durometer, typeA) 26 Elongation 50 (%) Tensile strength 0.4 (MPa) Tensile-shear bondstrength (glass) 0.11 (MPa) Specific gravity after curing 1.01 Volumeresistivity 5.0 (TΩ · m) Dielectric constant (50 Hz) 2.5 Dielectricdissipation factor (50 Hz) 0.0097 ³⁾Remarks: Curing conditions: Thecompostion was exposed for 5 seconds to a light from a high-pressuremercury lamp (80 W/cm) 10 cm distant from the composition. Thisirradiation was carried out three times.

The composition was applied on a part of the respective adherends ofmaterials shown in Table 5 below, and then cured under the respectivecuring conditions. Thereafter, the resulting piece of cured-film wasclawed with nails at their edge and at the interface between the curedfilm and the adherend to examine their adherence.

The results are shown below.

TABLE 5 Adherence Curing type UV Radiation + UV Radiation CondensationCondensation Adherends curing curing curing Aluminum ◯ ◯ ◯ Copper ◯ ◯ ◯Glass ◯ ◯ ◯ Epoxy resin ◯ ◯ ◯ Polycarbonate ◯ ◯ ◯ Acrylic resin ◯ ◯ ΔPBT ◯ ◯ Δ ◯: Good adhesion (i.e., No peeling occurred) Δ: A little pooradhesion (i.e., Slight peeling occurred)

As described above, the organosilicon compound of the present inventionprovides curing mechanisms in two ways for polymer compositions in whichit cures a composition based upon photopolymerization and in which itcures the composition by absorption of moisture in air. Hence, whenincorporated in silicone compositions, it acts as a cross-linking agenthaving well-balanced photopolymerizability and condensation curability.

1. An organosilicon compound represent by the following general formula(I):

wherein R¹ is a hydrogen atom, a phenyl group or a halogenated phenylgroup; R² is a hydrogen atom or a methyl group; R³'s may be the same ordifferent, and are each a substituted or unsubstituted monovalenthydrocarbon group having 1 to 10 carbon atoms; X is a hydrolyzablegroup; Z¹ is —R⁴—, —R⁴O— or —R⁴(CH₃)₂SiO—, where R⁴ is a substituted orunsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms,and, when the value of 3-m is plural, R⁴'s may be the same or different;Z² is an oxygen atom or a substituted or unsubstituted divalenthydrocarbon group having 1 to 10 carbon atoms; and m is 0 or 1 and n is0, 1 or
 2. 2. The compound according to claim 1, wherein R¹ is ahydrogen atom, a phenyl group or a halogenated phenyl group; R³ isselected from the up consisting of halogenated alkyl groups, alkylgroups, alkenyl groups, aryl groups, and aralkyl groups; X is selectedfrom the group consisting of alkoxyl groups, alkenyloxy groups, ketoximegroups, and acyloxy groups; R⁴ is selected from the group consisting ofhalogen-substituted alkylene groups, alkylene groups, and arylenegroups; and Z² is selected from the group consisting of an oxygen atom,halogen-substituted alkylene groups, alkylene groups, and arylenegroups.
 3. A compound which is represented by one of the followingformulas:


4. A compound according to claim 3, of the formula (a).
 5. A compoundaccording to claim 3, of the formula (b).
 6. A compound according toclaim 3, of the formula (c).
 7. A compound according to claim 3, of theformula (d).
 8. A compound according to claim 3, of the formula (e). 9.A compound according to claim 3, of the formula (f).
 10. A compoundaccording to claim 3, of the formula (g).
 11. A compound according toclaim 3, of the formula (h).
 12. A compound according to claim 3, of theformula (i).
 13. A compound according to claim 3, of the formula (j).14. A compound according to claim 3, of the formula (k).
 15. A compoundaccording to claim 3, of the formula (I).
 16. A compound according toclaim 3, of the formula (m).
 17. A compound according to claim 3, of theformula (n).
 18. A method comprising cross-linking a siliconecomposition with an organosilicon compound according to claim
 1. 19. Amethod comprising cross-linking a silicone composition with anorganosilicon compound according to claim
 2. 20. A method comprisingcross-linking a silicone composition with an organosilicon compoundaccording to claim
 3. 21. An organosilicon compound represented by thefollowing general formula (I):

wherein R¹ is a hydrogen atom, a phenyl group or a halogenated phenylgroup; R² is a hydrogen atom or a methyl group; R³'s may be the same ordifferent, and are each a substituted or unsubstituted monovalenthydrocarbon group having 1 to 10 carbon atoms; X is a hydrolyzablegroup; Z¹ is —R⁴—, —R⁴O— or —R⁴(CH₃)₂SiO—, where R⁴ is a substituted orunsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms,and, when the value of 3-m is plural, R⁴'s may be the same or different;Z² is a substituted or unsubstituted divalent hydrocarbon group having 1to 10 carbon atoms; and m is 0, 1 or 2 an n is 0, 1 or
 2. 22. Anorganosilicon compound represented by the following general formula (I):

wherein R¹ is a hydrogen atom, a phenyl group or a halogenated phenylgroup ; R² is a hydrogen atom or a methyl group; R³'s may be the same ordifferent, and are each a substituted or unsubstituted monovalenthydrocarbon group having 1 to 10 carbon atoms; X is a hydrolyzablegroup; Z¹ is —R⁴—, —R⁴O— or —R⁴(CH₃)₂SiO—, where R⁴ is a methylenegroup; Z² is an oxygen atom; and m is 0, 1 or 2 and n is 0, 1 or 2.